A natural rubber sample which crystallizes after stretching normally shows stress relaxation associated with this crystallization and normally ends up at a stress lower than that of the fully amorphous rubber before crystallization. On the other hand, a natural rubber sample which crystallizes during stretching becomes more rigid as a result of the crystallization and the stress required to extend it to a given stretch increases substantially above the stress needed to extend the fully amorphous rubber to the same elongation. Even though the former effect has been modeled and studied by the likes of Flory (1947), the latter effect has not yet been properly modeled or studied. The difference between crystallization during or after stretching will be studied in this article based on a thermodynamic model developed by the author to capture the thermomechanical effects of crystallization in natural rubber. The two limit cases of very rapid and very slow extension to a given stretch are singled out for comparison of the equilibrium stress.

1.
Flory
P. J.
,
1997
, “
Thermodynamics of Crystallization in High Polymers, i. Crystallization Induced by Stretching
,”
Journal of Chemical Physics
, Vol.
15
pp.
397
408
.
2.
Flory, P. J., 1985, Volume iii, part 6. U. W. Suter by L. Mandelkern, J. E. Mark and D. Y. Yoon, eds., Selected Works of Paul J. Flory. Stanford University Press.
3.
Gent
A. N.
,
1954
, “
Crystallization and the Relaxation of Stress in Stretched Natural Rubber Vulcanizates
,”
Trans. Faraday Soc.
,
50
:
51
51
.
4.
Leitner
M.
,
1955
, “
Young’s Modulus of Crystalline, Unstretched Rubber
,”
Trans. Faraday Soc.
,
51
:
1015
1015
.
5.
Magill
J. H.
,
1995
, “
Crystallization and Morphology of Rubber
,”
Rubber Chemistry and Technology
,
68
:
507
539
.
6.
Mandelkern, L., 1964, Crystallization of Polymers, McGraw-Hill, New York.
7.
Min, B. K., 1976, “Dynamic Behavior of Some Solids and Liquids,” PhD thesis, Brown University, Providence, RI.
8.
Negahban
M.
,
1997
, “
Thermodynamic Modeling of the Thermomechanical Effects of Polymer Crystalliation: A General Theoretical Structure
,”
International Journal of Engineering Science
,
35
:
227
298
.
9.
Stevenson
A.
,
1983
, “
The Influence of Low-Temperature Crystallization on the Tensile Elastic Modulus of Natural Rubber
,”
Journal of Polymer Science: Polymer Physics Edition
,
21
:
553
572
.
10.
Stevenson, A., 1989, “Crystallization in Elastomers at Low Temperatures,” Nicholas P. Cheriemisinoff, ed., Handbook of Polymer Science and Technology: Volume 2; Performance Properties of Plastics and Elastomers, pp. 61–99, Marcel Dekker.
11.
Treloar, L. R. G., 1975, The Physics of Rubber Elasticity, Clarendon Press, Oxford.
12.
Van Krevelen, D. W., and Hoftyzer, P. J., 1976, Properties of Polymers: Their Estimation and Correlation with Chemical Structure, Elsevier Scientific Publishing Company, Amsterdam.
13.
Wunderlich, B., 1973, Macromolecular Physics, 1: Crystal Structure, Morphology, Defects, Academic Press.
14.
Wunderlich, B., 1976, Macromolecular Physics, Volume 2: Crystal Nucleation, Growth, Annealing, Academic Press.
15.
Wunderlich, B., 1980, Macromolecular Physics, Volume 3: Crystal Melting, Academic Press.
16.
Ziabicki
A.
,
1996
a, “
Crystallization of Polymers in Variable External Conditions: 1. General Equations
,”
Colloid & Polymer Science
,
274
:
209
217
.
17.
Ziabicki
A.
,
1996
b, “
Crystallization of Polymers in Variable External Conditions: 1. Effects of Cooling in the Absence of Stress and Orientation
,”
Colloid & Polymer Science
,
274
:
705
716
.
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